Organic semiconductors are solids whose building blocks are pi-bonded molecules or polymers made up by carbon and hydrogen atoms and – at times – heteroatoms such as nitrogen, sulfur and oxygen. They exist in form of molecular crystals or amorphous thin films. In general, they are electrical insulators, but become semiconducting when charges are either injected from appropriate electrodes, upon doping or by photoexcitation. Organic semiconductors are solids whose building blocks are pi-bonded molecules or polymers made up by carbon and hydrogen atoms and – at times – heteroatoms such as nitrogen, sulfur and oxygen. They exist in form of molecular crystals or amorphous thin films. In general, they are electrical insulators, but become semiconducting when charges are either injected from appropriate electrodes, upon doping or by photoexcitation. In molecular crystals the energetic separation between the top of the valence band and the bottom conduction band, i.e. the band gap, is typically 2.5–4 eV, while in inorganic semiconductors the band gaps are typically 1–2 eV. This implies that they are, in fact, insulators rather than semiconductors in the conventional sense. They become semiconducting only when charge carriers are either injected from the electrodes or generated by intentional or unintentional doping. Charge carriers can also be generated in the course of optical excitation. It is important to realize, however, that the primary optical excitations are neutral excitons with a Coulomb-binding energy of typically 0.5–1.0 eV. The reason is that in organic semiconductors their dielectric constants are as low as 3–4. This impedes efficient photogeneration of charge carriers in neat systems in the bulk. Efficient photogeneration can only occur in binary systems due to charge transfer between donor and acceptor moieties. Otherwise neutral excitons decay radiatively to the ground state – thereby emitting photoluminescence – or non-radiatively. The optical absorption edge of organic semiconductors is typically 1.7–3 eV, equivalent to a spectral range from 700 to 400 nm (which corresponds to the visible spectrum). In 1862, Henry Letheby obtained a partly conductive material by anodic oxidation of aniline in sulfuric acid. The material was probably polyaniline. In the 1950s, researchers discovered that polycyclic aromatic compounds formed semi-conducting charge-transfer complex salts with halogens. In particular, high conductivity of 0.12 S/cm was reported in perylene–iodine complex in 1954. This finding indicated that organic compounds could carry current. The fact that organic semiconductors are, in principle, insulators but become semiconducting when charge carriers are injected from the electrode(s) was discovered by Kallmann and Pope. They found that a hole current can flow through an anthracene crystal contacted with a positively biased electrolyte containing iodine that can act as a hole injector. This work was stimulated by the earlier discovery by Akamatu et al. that aromatic hydrocarbons become conductive when blended with molecular iodine because a charge-transfer complex is formed. Since it was readily realized that the crucial parameter that controls injection is the work function of the electrode, it was straightforward to replace the electrolyte by a solid metallic or semiconducting contact with an appropriate work function. When both electrons and holes are injected from opposite contacts, they can recombine radiatively and emit light (electroluminescence). It was observed in organic crystals in 1965 by Sano et al. In 1972, researchers found metallic conductivity in the charge-transfer complex TTF-TCNQ. Superconductivity in charge-transfer complexes was first reported in the Bechgaard salt (TMTSF)2PF6 in 1980. In 1973 Dr. John McGinness produced the first device incorporating an organic semiconductor. This occurred roughly eight years before the next such device was created. The 'melanin (polyacetylenes) bistable switch' currently is part of the chips collection of the Smithsonian Institution. In 1977, Shirakawa et al. reported high conductivity in oxidized and iodine-doped polyacetylene. They received the 2000 Nobel prize in Chemistry for 'The discovery and development of conductive polymers'. Similarly, highly conductive polypyrrole was rediscovered in 1979. Rigid-backbone organic semiconductors are now used as active elements in optoelectronic devices such as organic light-emitting diodes (OLED), organic solar cells, organic field-effect transistors (OFET), electrochemical transistors and recently in biosensing applications. Organic semiconductors have many advantages, such as easy fabrication, mechanical flexibility, and low cost. The discovery by Kallman and Pope paved the way for applying organic solids as active elements in semiconducting electronic devices, such as organic light-emitting diodes (OLEDs) that rely on the recombination of electrons and hole injected from 'ohmic' electrodes, i.e. electrodes with unlimited supply of charge carriers. The next major step towards the technological exploitation of the phenomenon of electron and hole injection into a non-crystalline organic semiconductor was the work by Tang and Van Slyke. They showed that efficient electroluminescence can be generated in a vapor-deposited thin amorphous bilayer of an aromatic diamine (TAPC) and Alq3 sandwiched between an indium-tin-oxide (ITO) anode and an Mg:Ag cathode. Another milestone towards the development of organic light-emitting diodes (OLEDs) was the recognition that also conjugated polymers can be used as active materials. The efficiency of OLEDs was greatly improved when realizing that phosphorescent states (triplet excitons) may be used for emission when doping an organic semiconductor matrix with a phosphorescent dye, such as complexes of iridium with strong spin–orbit coupling.